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However, the formation of energy\u2010dense liquid fuels such as methanol remains rare, particularly under low\u2010temperature and low\u2010pressure conditions that can be coupled to renewable electricity sources via electrochemistry. Here, a multicatalyst system pairing an electrocatalyst with a thermal organometallic catalyst is introduced, which enables the reduction of CO\n                    <jats:sub>2<\/jats:sub>\n                    to methanol at ambient temperature and pressure. The cascade methanol synthesis proceeds via CO\n                    <jats:sub>2<\/jats:sub>\n                    reduction to formate by electrocatalyst [Cp*Ir(bpy)Cl]\n                    <jats:sup>+<\/jats:sup>\n                    (Cp*=pentamethylcyclopentadienyl, bpy=2,2\u2032\u2010bipyridine), Fischer esterification of formate to isopropyl formate catalyzed by trifluoromethanesulfonic acid (HOTf), and thermal transfer hydrogenation of isopropyl formate to methanol facilitated by the organometallic catalyst (H\u2010PNP)Ir(H)\n                    <jats:sub>3<\/jats:sub>\n                    (H\u2010PNP=HN(C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>4<\/jats:sub>\n                    P\n                    <jats:sup>i<\/jats:sup>\n                    Pr\n                    <jats:sub>2<\/jats:sub>\n                    )\n                    <jats:sub>2<\/jats:sub>\n                    ). The isopropanol solvent plays several crucial roles: activating formate ion as isopropyl formate, donating hydrogen for the reduction of formate ester to methanol via transfer hydrogenation, and lowering the barrier for transfer hydrogenation through hydrogen bonding interactions. In addition to reporting a method for room\u2010temperature reduction of challenging ester substrates, this work provides a prototype for pairing electrochemical and thermal organometallic reactions that will guide the design and development of multicatalyst cascades.\n                  <\/jats:p>","DOI":"10.1002\/anie.202416061","type":"journal-article","created":{"date-parts":[[2024,11,21]],"date-time":"2024-11-21T15:04:29Z","timestamp":1732201469000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":9,"title":["Room\u2010Temperature Formate Ester Transfer Hydrogenation Enables an Electrochemical\/Thermal Organometallic Cascade for Methanol Synthesis from CO\n                    <sub>2<\/sub>"],"prefix":"10.1002","volume":"64","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-1620-8514","authenticated-orcid":false,"given":"Sergio","family":"Fern\u00e1ndez","sequence":"first","affiliation":[{"name":"Department of Chemistry University of North Carolina at Chapel Hill  Chapel Hill North Carolina 27599\u20133290 United States"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5507-7791","authenticated-orcid":false,"given":"Eric A.","family":"Assaf","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of North Carolina at Chapel Hill  Chapel Hill North Carolina 27599\u20133290 United States"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shahbaz","family":"Ahmad","sequence":"additional","affiliation":[{"name":"Chemistry Division, Energy &amp; Photon Sciences Brookhaven National Laboratory  Upton New York 11973 United States"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0008-1835-548X","authenticated-orcid":false,"given":"Benjamin D.","family":"Travis","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of North Carolina at Chapel Hill  Chapel Hill North Carolina 27599\u20133290 United States"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Julia B.","family":"Curley","sequence":"additional","affiliation":[{"name":"Department of Chemistry Yale University  P.O. Box 208107 New Haven Connecticut 06520, United States"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8337-198X","authenticated-orcid":false,"given":"Nilay","family":"Hazari","sequence":"additional","affiliation":[{"name":"Department of Chemistry Yale University  P.O. Box 208107 New Haven Connecticut 06520, United States"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1994-9024","authenticated-orcid":false,"given":"Mehmed Z.","family":"Ertem","sequence":"additional","affiliation":[{"name":"Chemistry Division, Energy &amp; Photon Sciences Brookhaven National Laboratory  Upton New York 11973 United States"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9390-3951","authenticated-orcid":false,"given":"Alexander J. 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